Dithianyl anilids

ABSTRACT

This invention discloses new compounds of the formula   WHEREIN Y is selected from the group consisting of hydrogen, lower alkyl and halogen; R1 is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; R2 is lower alkyl; R3, R4, R5, R6 and R7 are independently selected from the group consisting of hydrogen and lower alkyl; X is halogen, m is an integer from 0 to 2; Z1 and Z2 are independently selected from the group consisting of oxygen and sulfur; and n is an integer from 1 to 2. The compounds of the above description are useful as herbicides.

United States Patent [191 Richter et al.

[ DITHIANYL ANILIDS [75] Inventors: Sidney B. Richter, Chicago; John Krenzer, Oak Park, both of I11.

[73] Assignee: Velsicol Chemical Corporation,

Chicago, Ill.

[22] Filed: June 3, 1974 [2!] Appl. No.: 475,542

Related US. Application Data [62] Division of Ser. No 357,746, May 7, 1973.

[52] US. Cl 260/327 M [51] int. Cl C07d 73/00 [58] Field of Search 260/327 M [56] References Cited UNITED STATES PATENTS 3,759,952 9/1973 Teach 260/327 3,772,334 11/1973 Teach 260/327 Primary liraminerHenry R. .Iiles Assistant ExaminerC. M. S. Jaisle Atmrney, Agent, or Firm-Robert J. Schwarz; Dietmar H. Olesch [57] ABSTRACT This invention discloses new compounds of the for- Aug. 19, 1975 mula wherein Y is selected from the group consisting of hydrogen, lower alkyl and halogen; R is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; R is lower alkyl; R, R R R and R are independently selected from the group consisting of hydrogen and lower alkyl; X is halogen, m is an integer from O to 2; Z and Z are independently selected from the group consisting of oxygen and sulfur; and n is an integer from 1 to 2. The compounds of the above description are useful as herbicides.

2 Claims, No Drawings 1 2 DITHIANYL ANILIDS this time the reaction mixture can be washed with This application is a divisional application of our cowater to remove inorganic salts and stripped of solvent pending application Ser. No. 357,746, filed May 7, to yield the desired product. This product can be used 1973. as such or can be further purified by recrystallization This invention relates to new compositions of matter or other conventional means. and more specifically relates to new compounds of the The compounds of formula ll can be prepared by reformula acting a substituted aniline of the formula z c R l (CH Cl-l (CH I 2 6 N Z C R l c CHX R Y H l l O R R (I I wherein Y is selected from the group consisting of hy- 2 drogen, lower alkyl and halogen; R is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; R is lower alkyl; R, R", R R and R are independently selected from the group consisting of hydrogen and lower alkyl; X is halogen, m is an integer from NH O to 2; Z and Z are independently selected from the group consisting of oxygen and sulfur; and n is an integer from 1 to 2. Y

The term lower as used herein designates a straight 1 (IV) or branched carbon chain of up to four carbon atoms.

The compounds of the present invention are unexpectedly useful as herbicides and are particularly useful in controlling grassy weeds.

In a preferred embodiment of the present invention Y is hydrogen, X is chlorine or bromine, and at least two of R, R R and R are hydrogen. 7

The compounds of the present invention can be prewherein Y, R and R are as heretofore described, with pared by reacting a compound of the formula a compound of the formula R l Z:L C R5 l N '(CH CH (CH l I H Z c R Y I l 1 R R (II) wherein Y, R, R R, R R R, Z, Z n and m are as heretofore described, with an a-haloalkanoyl chloride of the formula C o I Hal (CH cu (CH c1 c CHX l I z c R R (III) I R V wherein X and R are as heretofore described. This reaction can be effected by combining a compound of wherein Hal designates halogen such as chlorine or formula II with a compound of formula Ill in an inert bromine and wherein Z, 2*, R, R R, R n and m are organic reaction medium, such as dioxane, in the presas heretofore described. This reaction can be effected ence of an acid acceptor, such as an alkali metal carby combining a compound of formula IV with a combonate or bicarbonate at a temperature of from about pound of formula V in an inert organic reaction mix- 10C to about 25C and stirring the resulting mixture ture such as dimethylformamide in the presence of an for a period of about 15 to about minutes. After acid acceptor such as an alkali metal carbonate or bi- OCH Cl (CH CH OCH wherein n is as heretofore described, with a diol or dithiol of the formula I 4 7 R (c11 c R I I Z 2 2 H (VII) wherein R, R R R Z, Z and m are as heretofore described. This reaction can be effected by combining the compound of formula V] with the compound of formula VII in about equimolar amounts and in the presence of an acid catalyst, such as sulfuric acid or toluene sulfonic acid, under anhydrous conditions. The mixture can be heated at reflux for a period of from about 1 to about 4 hours. After this time the reaction mixture can be distilled under reduced pressure to yield the desired product.

Exemplary diols and dithiols of formula VII useful for preparing the compounds of formula V are ethandiol- 1,2, propandiol-l,2, propandiol-l ,3, butandiol-l,2, butandiol-l,3, butandiol-l,4, butandiol-",3, pentandiol-l,2, pentandiol-l,3, pentandiol-l,4, pentandiol-2,3, pentandiol-2,4, 2-methyl-pentandiol-2,4, 2-methyl propandioll ,2, 2-methylbutandiol-2,3 3-methylbutandiol-l ,3, hexandiol-l,2, hexandiol-l,3, hexandiol-l ,4, hexandiol-2,3, hexandiol-2,4, hexandiol-2,5, hexandiol-3,4, 3-methylhexandiol-3,4, 3-ethylhexandiol-3,4, ethandithiol-l ,2, propandithiol-l ,2, propandithiol-l ,3, butandithioll ,2, butandithioll ,3, butandithioll ,4, butandithiol-2,3, pentandithiol-l,2 and the like.

Exemplary substituted anilines of formula IV useful for preparing the compounds of formula II are 2- methylaniline, 2-ethylaniline, 2-propylaniline, 2- isopropylaniline, 2-butylaniline, 2,6-dimethylaniline, 2,6-diethylaniline, 2,6-dipropylaniline, 2,6 dibutylaniline, 2-methoxy-6-methylaniline, Z-methoxy- 6-ethylaniline, 2-ethoxy-6-methylaniline, 2ethoxy-6- ethylaniline, 2-propoxy-6methylaniline, 2-butoxy-6- ethylaniline, 2,4,6-trimethylaniline, 2,4,5- triethylaniline, 2,4,6-tripropylaniline, 2,6dimethyl-4 butylaniline, 2,4-dimethylaniline, 2,4-diethylaniline, 2-methyl-4-chloroaniline, 2-ethyl3-bromoaniline, 2,6-dimethyl-4-iodoaniline, 2,6-diethyl-4-chloroaniline and the like.

Exemplary a-haloalkanoyl chlorides of formula III are chloroacetyl chloride, bromoacetyl chloride, iodoacetyl chloride, oz-chloropropanoyl chloride, a-bromopropanoyl chloride, a-chlorobutanoyl chloride, ozchlo ropentanoyl chloride, a-chlorohexanoyl chloride and the like.

The preparation of the compounds of the present invention is more specifically illustrated in the following examples.

4 EXAMPLE 1 Preparation of 2-Chloromethyl-l ,3-dioxolane The dimethyl acetal of 2-chloroacetaldehyde (125 grams; 1.0 mole) and ethandiol-l ,2 (62 grams; 1.0 mole) are charged into a glass reaction flask equipped with a mechanical stirrer, thermometer and reflux condenser. Toluene sulfonic acid (0.3 grams) is added to the flask and the reaction mixture is refluxed for a period of about 2 hours. After this time the reaction mixture is distilled under aspirator partial pressure to remove methanol yielding the desired product 2-chloromethyll ,3-dioxolane.

EXAMPLE2 Preparation of N-( l ,3-Dioxolan-2-ylmethyl )-2,6-dimethylaniline 2,6-Dimethylaniline grams), 2-chloromethyll ,3- dioxolane (25 grams), potassium carbonate (34 grams) and dimethylformamide (50 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated at reflux for a period of about 18 hours. After this time the mixture was filtered and distilled to yield the desired product N-( l,3-dioxolan-2- ylmethyl)-2,6-dimethylaniline.

EXAMPLE 3 Preparation of N-a-Chloroacetyl-N-( l,3-dioxolan-2-ylmethyl)-2,6-

dimethylaniline N-( l,3-Dioxolan-2-ylmethyl)-2,6-dimethylaniline (7.8 grams), sodium bicarbonate. (7.0 grams), dioxane (20 ml) and water (4 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture was cooled to a temperature of about 0C and chloroacetyl chloride (5.0 grams) was added, with stirring, over a period of about 15 minutes. After the addition was completed stirring was continued for a period of about 1 hour. After this time ether ml) was added to the mixture and the resulting solution was washed with water. The washed solution was then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue was recrystallized from an ether-pentane mixture to yield the desired product N-oz-chloroacetyl-N-( 1,3- dioxolan-Z-ylmethyl)-2,6-dimethylaniline having a melting point of 58 to 60C.

EXAMPLE 4 Preparation of N-( l ,3-Dioxolan2-ylmethyl)-2,6-diethylaniline 2,6-Diethylaniline 75 grams; 0.5 mole), Z-chloromethyl-l,3-dioxolane (25 grams; 0.2 mole), potassium carbonate (22 grams; 0.2 mole) and dimethylformamide (50 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture was heated, with stirring, for a period of about 18 hours. After this time the reaction mixture was filtered and then distilled to yield the desired product N-(l,3- dioxolan-2-ylmethyl)2,6-diethylaniline.

EXAMPLE 5 Preparation of N-a-ChloroacetyI-N-( l,3dioxolan-2ylmethyl )-2,6 diethylaniline N-( 1,3-dioxolan-2-ylmethyl)-2,6-diethylaniline (7.7 grams), sodium bicarbonate (6.0 grams), dioxane (20 ml) and water (4 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. This mixture was cooled to a temperature of about C and chloroacetyl chloride (4.0 grams) was added, with stirring, over a period of about 15 minutes. After the addition was completed stirring was continued for a period of about 1 hour. After this time ether 100 ml) was added to the mixture and the resulting solution was washed with water. The washed solution was then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue was recrystallized from an ether-pentane mixture to yield the desired product N-a-chloroacetyl-N-( 1 ,3- dioxolan-Z-ylmethyl)-2,6-diethylaniline having a melting point of 86 to 87C.

EXAMPLE 6 Preparation of N-( l,3-Dioxolan-2-ylmethyl)-2-methyl-5-chloroaniline 2-Methyl-S-chloroaniline (75 grams), 2-chloromethyl-1,3-dioxolane (25 grams), potassium carbonate (22 grams) and dimethylformamide (50 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer, and reflux condenser. The reaction mixture was heated, with stirring, for a period of about 26 hours. After this time the reaction mixture was filtered and then distilled to yield the desired product N-(1,3-dioxolan-2-ylmethyl)-2methyl-5-chloroani1ine having a boiling point of 1 16 to 1 18C at 0.1 mm of Hg pressure.

EXAMPLE 7 Preparation of N-a-Chloroacetyl-N-( l ,3-dioxolan-2-ylmethyl)-2- methyl-S-chloroaniline N-( 1,3Dioxolan2-ylmethyl)-2-methyl-5- chloroaniline (8 grams), sodium bicarbonate (7 grams), dioxane (50 ml) and water (4 ml) were charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. This mixture was cooled to a temperature of about 0C and chloroacetyl chloride (4.3 grams) was added, with stirring, over a period of about minutes. After the addition was completed stirring was continued for a period of about 1 hour. After this time ether 100 ml) was added to the mixture and the resulting solution was washed with water. The washed solution was then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue was recrystallized from hexane to yield the desired product N-a-chloroacetyl- N-( 1,3-dioxolan-2-ylmethyl)-2-methyl-5-chloroaniline having a melting point of 88 to 89C.

EXAMPLE 8 Preparation of 2-Chloromethyl-1,3-dithiepane The dimethyl acetal of 2-chloroacetaldehyde 125 grams; 1.0 mole) and butandithiol-1,4 (122 grams; 1.0 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. Toluene sulfonic acid (0.3 grams) is added to the reaction mixture and the mixture is refluxed for a period of about 2 hours. After this time the reaction mixture is distilled under aspirator pressure to yield the desired product 2-chloromethyl- 1 ,3-dithiepane.

EXAMPLE 9 Preparation of N-( l ,3-Dithiepan-2-ylmethyl )2,6-diethylaniline 2,6-Diethylaniline grams), 2-chloromethyl-1,3

dithiepane (36.5 grams), potassium carbonate (34 grams) and dimethylformamide (75 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of about 18 hours. After this time the mixture is filtered and distilled to yield the desired product N-(1,3-dithiepan-2- ylmethyl)-2,6-diethylaniline.

EXAMPLE 10 Preparation of N-oz-Chloroacetyl-N-( 1 ,3-dithiepan'2-ylmethyl )-2,6- diethylaniline N-( 1,3-Dithiepan-2-ylmethyl)-2,6-diethylaniline 15 grams), sodium bicarbonate (10 grams), dioxane (30 ml) and water (5 m1) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture is cooled to a temperature of about 0C and chloroacetyl chloride (7 grams) is added, with stirring, over a period of about 15 minutes. After the addition is completed stirring is continued for a period of about 1 hour. After this time ether ml) is added to the mixture and the resulting solution is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue is recrystallized to yield the desired product N-a-chloroacetyl-N- 1,3-dithiepan-2-ylmethyl)-2,6-diethylaniline.

EXAMPLE 11 Preparation of 2-Chloromethyl-1,3-dioxane The dimethyl acetal of 2-chloroacetaldehyde grams; 1.0 mole) and propandiol-1,3 (76 grams; 1.0 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux conden'ser. Toluene sulfonic acid (0.3 grams) is added to the reaction mixture and the mixture is refluxed for a period of about 3 hours. After this time the reaction mixture is distilled under aspirator pressure to yield the desired product 2-chloromethyl1,3-dioxane.

EXAMPLE 1 2 Preparation of N-( 1 ,3-dioxan-2-ylmethyl)-2,6-diethylaniline 2,6-Diethylaniline (75 grams), 2-chloromethyl-l,3- dioxane (14 grams), potassium carbonate (34 grams) and dimethylformamide (60 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of about 18 hours. After this time the mixture is filtered and distilled to yield the desired product N-(1,3-dioxan-2- ylmethyl)-2,6-diethylaniline.

EXAMPLE 13 Preparation of N-a-Chloroacetyl-N-( l ,3-dioxan-2-ylmethyl)-2,6- diethylaniline N-( l ,3-Dioxan-2-ylmethyl)-2,6-diethylaniline (25 grams), sodium bicarbonate (10 grams), dioxane (30 ml) and water (4 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture is cooled to a temperature of about C and chloroacetyl chloride grams) is added, with stirring, over a period of about 15 minutes. After the addition is completed stirring is continued for a period of about 1 hour. After this time ether 100 ml) is added to the mixture and the resulting solution is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue is recrystallized to yield the desired product N-a-chloroacetyl-N- l ,3-dioxan-2-ylmethyl)-2,6-diethylaniline.

EXAMPLE 14 Preparation of 2-Chloromethyll ,3-dioxepane The dimethyl acetal of 2-chloroacetaldehyde (125 grams; 1.0 mole) and butandiol-l ,4 (90 grams; 1.0 mole) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. Toluene sulfonic acid (0.3 grams) is added to the reaction mixture and the mixture is refluxed for a period of about 3 hours. After this time the reaction mixture is distilled under aspirator pressure to yield the desired product 2-chloromethyl-1,3-dioxepane.

EXAMPLE 15 Preparation of N-( l ,3Dioxepan-2-ylmethyl)-2,6-diethylaniline 2,6-Diethylaniline (75 grams), 2-chloromethyl-1,3- dioxepane (15 grams), potassium carbonate (34 grams) and dimethylformamide (60 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer, thermometer and reflux condenser. The reaction mixture is heated at reflux for a period of about 18 hours. After this time the mixture is filtered and distilled to yield the desired product N-( 1,3-dioxepan-2- ylmethyl)-2,6-diethylaniline.

EXAMPLE 16 Preparation of N-u-Chloroacetyl-N-( 1,3-dioxepan-2-ylmethyl)-2,6- diethylaniline N-( l,3-dioxepan2-ylmethyl )-2,6-diethylaniline (26.3 grams), sodium bicarbonate 15 grams), dioxane ml) and water (4 ml) are charged into a glass reaction vessel equipped with a mechanical stirrer and thermometer. The mixture is cooled to a temperature of about 0C and chloroacetyl chloride (15 grams) is added, with stirring, over a period of about 15 minutes. After the addition is completed stirring is continued for a period of about 1 hour. After this time ether 100 ml) is added to the mixture and the resulting solution is washed with water. The washed solution is then dried over anhydrous magnesium sulfate and stripped of solvents leaving a solid residue. The residue is recrystallized to yield the desired product N-a-chloroacetyl-N- l ,3-dioxepan-2-ylmethyl)-2,6-dicthylaniline.

Additional compounds within the scope of the present invention can be prepared by the procedures detailed in the foregoing examples. In the following examples are given the essential starting materials required to prepare the indicated named compounds by the methods heretofore described.

EXAMPLE [7 The dimethyl acetal of 2-chloroacetaldehyde ethandiol-l,2 methylaniline chloroacetyl chloride N-a-chloroacetyl-N-( 1,3-dioxolan-2-ylmethyl)-2- methylaniline.

EXAMPLE 1 8 The dimethyl acetal of 2-chloroacetaldehyde ethandiol-l,2 2-ethylaniline chloroacetyl chloride N-oz-chloroacetyl-N-( l ,3-dioxolan-2-ylmethyl)-2- ethylaniline.

EXAMPLE 19 The dimethyl acetal of 3-chloropropionaldehyde ethandiol-1,2 2,6-diethylaniline chloroacetyl chloride N-a-chloroacetyl-N-( 1 ,3-dioxolan-2-ylethyl 2,6-diethylaniline.

EXAMPLE 20 The dimethyl acetal of 2-chloroacetaldehyde propandiol-1,2 2,4dimethylaniline bromoacetyl chloride N-oz-bromoacetyl-N-(4methyl-1,3-dioxolan-2- ylmethyl)-2,4-dirnethylaniline.

EXAMPLE 2 1 The dimethyl acetal of 2-chloroacetaldehyde butandiol-1,2 2-propyl-4-bromoaniline a-chloropropanoyl chloride N-a-chloropropionyl-N-( 4-ethyll ,3-dioxolan-2-ylmethyl )-2-propyl-4-bromoaniline.

EXAMPLE 22 etyl chloride N-a-chloroacetyl-N-(4-butyl-1 ,3- dioxolan-2-ylmethyl)-2-methyl-6-methoxyaniline.

EXAMPLE 24 The dimethyl acetal of 2-chloroacetaldehyde hexandiol-3,4 2,3-diethyl6-ethoxyaniline oz-chlorobutanoyl chloride N-achlorobutanoyl-N-(4,5-diethyll,3-dioxolan-2-ylmethyl)-2,3-diethyl-6-ethoxyaniline.

EXAMPLE 25 The dimethyl acetal of 2-chloroacetaldehyde propandiol-1,3 2-methyl-4-iodoaniline iodoacetyl chloride N-a-iodoacetyl-N-( l ,3-dioxan-2-ylmethyl)- 2-methyl-4-iodoaniline.

EXAMPLE 26 The dimethyl acetal of 2-chloroacetaldehyde butandiol-l ,3 2-methyl-6-butoxyaniline chloroacetyl chloride Na-chloroacetyl-N-( 4-methyl-l ,3- dioxan-2-ylmethyl)-2-methyl-6-butoxyaniline.

EXAMPLE 27 The dimethyl acetal of 2-chloroacetaldehyde butandiol-l ,4 2-propyl4-ethylaniline a-chlorohexanoyl chloride N-a-chlorohexanoyl-N-( l ,3- dioxepan-Z-ylmethyl)-2-propyl-4-ethylaniline.

The dimethyl acetal of 2-chloroacetaldehyde ethandithiol-l,2 2,6-dimethylaniline chloroacetyl chloride N-a-chloroacetyl-N-( 1,3-dithiolan-2- ylmethyl )-2,6-dimethylaniline.

EXAMPLE 29 The dimethyl acetal of 2-chloroacetaldehyde propandithiol-l,3 2,6-diethylaniline chloroacetyl chloride N-a-chloroacetyl-N-( 1,3-dithian-2- ylmethyl )-2,6-diethylaniline.

For practical use as herbicides the compounds of this invention are generally incorporated into herbicidal compositions which comprise an inert carrier and a herbicidally toxic amount of such a compound. Such herbicidal compositions, which can also be called formulations, enable the active compound to be applied conveniently to the site of the weed infestation in any desired quantity. These compositions can be solids such as dusts, granules, or wettable powders; or they can be liquids such as solutions, aerosols, or emulsifiable concentrates.

For example, dusts can be prepared by grinding and blending the active compound with a solid inert carrier such as the talcs, clays, silicas, pyrophyllite, and the like. Granular formulations can be prepared by impregnating the compound, usually dissolved in a suitable solvent, onto and into granulated carriers such as the attapulgites or the vermiculites, usually of a particle size range of from about 0.3 to 1.5 mm. wettable powders, which can be dispersed in water or oil to any desired concentration of the active compound, can be prepared by incorporating wetting agents into concentrated dust compositions.

In some cases the active compounds are sufficiently soluble in common organic solvents such as kerosene or xylene so that they can be used directly as solutions in these solvents. Frequently, solutions of herbicides can be dispersed under super-atmospheric pressure as aerosols. However, preferred liquid herbicidal compo sitions are emulsifiable concentrates, which comprise an active compound according to this invention and as the inert carrier, a solvent and an emulsifier. Such emulsifiable concentrates can be extended with water and/or oil to any desired concentration of active compound for application as sprays to the site of the weed infestation. The emulsifiers most commonly used in these concentrates are nonionic or mixtures of nonionic with anionic surface-active agents. With the use of some emulsifier systems an inverted emulsion (water in oil) can be prepared for direct application to weed infestations.

A typical herbicidal composition according to this invention is illustrated by the following example, in

.which the quantities are in parts by weight.

EXAMPLE 30 Preparation of a Dust Product of Example 3 Powdered Talc The above ingredients are mixed in a mechanical grinder-blender and are ground until a homogeneous,

method for the control of weeds comprises contacting the locus of said weeds with a herbicidal composition comprising an inert carrier and as an essential active ingredient, in a quantity which is herbicidally toxic to said weeds, a compound of the present invention. Theconcentration of the new compounds of this invention in the herbicidal compositions will vary greatly with the type of formulation and the purpose for which it is designed, but generally the herbicidal compositions will comprise from about 0.05 to about 95 percent by weight of the active compounds of this invention. In a preferred embodiment of this invention, the herbicidal compositions will comprise from about 5 to about percent by weight of the active compound. The compositions can also comprise such additionalsubstances as other pesticides, such as insecticides, nematocides, fungicides, and the like; stabilizers, spreaders, deactivators, adhesives, stickers, fertilizers, activators, synergists, and the like.

The compounds of the present invention are also useful when combined with other herbicides and/or defoliants, dessicants, growth inhibitors, and the like in the herbicidal compositions heretofore described. These other materials can comprise from about 5% to about of the active ingredients in the herbicidal compositions. Use of combinations of these other herbicides and/or defoliants, dessicants, etc. with the compounds of the present invention provide herbicidal compositions which are more effective in controlling weeds and often provide results unattainable with separate compositions of the individual herbicides. The other herbicides, defoliants, dessicants and plant growth inhibitors, with which the compounds of this invention can be used in the herbicidal compositions to control weeds, can include chlorophenoxy herbicides such as 2,4-1), 2,4,5-T, MCPA, MCPB, 4(2,4-DB), 2,4-DEB, 4-CPB, 4-CPA, 4-CPP, 2,4,5-TB, 2,4,5-TES, 3,4-DA, silvex and the like; carbamate herbicides such as IPC, ClPC, swep, barban, BCPC, CEPC, CPPC, and the like; thiocarbamate and dithiocarbamate herbicides such as CDEC, metham sodium, EPT C, diallate, PEBC, perbulate, vernolate and the like; substituted urea herbicides such as norea, siduron, dichloral urea, chloroxuron, cycluron, fenuron, monuron, monuron TCA, diuron, linuron, monolinuron, neburon, buturon, trimeturon and the like; symmetrical triazine herbicides such as simazine, chlorazine, atraone, desmetryne, norazine, ipazine, prometryn, atazine, trietazine, simetone, prometone, propazine, ametryne and the like; chloroacetamide herbicides such as alpha-chloro-N, N- dimethylacetamide, CDEA, CDAA, alpha-chloro-N- isopropylacetamide, 2-chloro-N-isopropylacetanilide, 4-( chloroacetyl )morpholine, l- (chloroacetyl)piperidine, and the like; chlorinated aliphatic acid herbicides such as TCA, dalapon, 2,3- dichloropropionic acid, 2,2,3-TPA and the like; chlorinated benzoic acid and phenylacetic acid herbicides such as 2,3,6-TBA, 2,3,5,6-TBA, tricamba, amiden, fenac, PBA, 2-methoxy-3,-dichlorophenylacetic acid, 3-methoxy-2,6-dichlorophenylacetic acid, 2-methoxy- 3,5,o-trichlorophenylacetic acid, 2,4-dichloro-3- nitrobenzoic acid and the like; and such compounds as aminotriazole, maleic hydrazide, pheny] mercuric acetate, endothal, biuret, technical chlordane, dimethyl 2,3,5,6-tetrachloroterephthalate, diquat, erbon, DNC, PNBP, dichlobenil, DPA, diphenamid, dipropalin, trifluralin, solan, dicryl, merphos, DMPA, DSMA, MSMA, potassium azide, acrolein, benefin, bensulide, AMS, bromacil, 2-(3,4dichlorophenyl)-4-methyll,2,4-oxadiazolidine-3,S-dione, bromoxynil, cacodylic acid, CMA, CPMF, cypromid, DCB, DCPA, dichlone, diphenatril, DM'IT, DNAP, EBEP, EXD, HCA, ioxynil, IPX, isocil, potassium cyanate, MAA, MAMA,

one or two ounces of active compound per acre may be sufficient for good control of a light infestation of weeds growing under adverse conditions, the application of ten pounds or more of an active compound per the growth of such weeds without damaging beneficial plants or livestock.

The new compounds of this invention are particularly valuable for weed control because they are toxic to many species and groups of weeds while they are relatively nontoxic to many beneficial plants. The exact amount of compound required will depend on a variety of factors, including the hardiness of the particular weed species, weather, type of soil, method of application, the kind of beneficial plants in the same area, and the like. Thus, while the application of up to only about MCPES, MCPP, molinate, P q acre may be required for good control of a dense infes- Picloram, PCA, py $680116, tel'bacil, tation of hardy perennial weeds growing under favorterbutol, TCBA, brominil, (DP-50144, H-l76-l, H-732, able conditions.

M3901, Planavin, Sodium tetl'aborate, Calcium y The herbicidal activity of the compounds of this in- DEF, ethyl Xamhogen disulfide, Sindone, Sindone vention was demonstrated by experiments carried out pr p and the likefor the pre-emergence control of a variety of weeds. In Such herbicides can also be used in the methods and these experiments small plastic greenhouse pots filled compositions of this invention in the form of their salts, i h d il were d d i h h d d Twenty esters, amides, and other derivatives whenever applicaf hours o l after seeding the pots were sprayed ble to the Partllular F compoundswith water until the soil was wet and the test comweeds are undesirable Plants growing where y are pounds formulated as aqueous emulsions of acetone not Wanted, having no economic Value, and interfering solutions containing emulsifiers were sprayed at the in with the production of cultivated crops, ith the g dicated concentrations on the surface of the soil. g of Ornamental P With the Welfare of live- After spraying, the soil containers were placed in the stock. Many types of weeds are known, including annugreenhouse d id d ith supplementary heat a als Such as Plgweed, lambsquarters, foxtail cl'abgtass, required and daily or more frequent watering. The Wild mustard, field Pennycress, ryegrass, g -g plants were maintained under these conditions for a pe- Chickweed, Wild Oats, Velvetleaf, Purslane, barnyard riod of from to days, at which time the condition grass, Smartweed, knotweed, Cocklebuf, Wild buckof the plants and the degree of injury to the plants was Wheat, kOChia, medic, (30m cockle, ragweed, SOWthiS- rated on a scale of from O to 10, as follows: 0 no intle, coffeeweed, croton, cuphea, dodder, fumitory, 25 jury, 1,2 slight injury, 3,4 moderate injury, 5,6 grounds l, h mp n ttl kn p g p rry, emeX, moderately severe injury, 7,8,9 severe injury and 10 jungle rice, pondweed, dog fennel, carpetweed, morndeath. The effectiveness of these compounds is deming glory, bedstraw, ducksalad and naiad; biennials onstrated by the following data:

TABLE 1 Concentration of Test Yellow Johnson Yellow Bamyard Test Compound Compound in lbs/acre Nutsedge Grass Pigweed Foxtail grass Crabgrass Product of 10 10 9 10 10 l0 10 Example 3 4 l0 9 l0 9 10 10 2 10 10 1O 9 9 10 l 10 8 l0 8 9 9 Product of 10 10 9 10 10 10 10 Example 5 4 10 9 9 9 10 9 2 10 8 9 9 9 9 l 10 8 3 9 8 9 Product of Example 18 10 9 2 10 10 10 5 4 l0 1 l0 9 9 7 2 10 0 9 9 8 5 1 t0 0 3 8 4 such as wild carrot, matricaria, wild barley, campion, We claim: chamomile, burdock, mullein, roundleaved mallow, l. A compound of the formula bull thistle, hounds-tongue, moth mullein and purple 4 star thistle; or perennials such as white cockle, peren- R nial ryegrass, quackgrass, Johnson grass, Canada this- 1 l 5 2 c P. tle, hedge bindweed, Bermuda grass, sheep sorrel, cur ley dock, nutgrass, field chickweed, dandelion, cam- (CH CH A panula, field bindweed, Russian knapweed, mesquite, 2 n I 2 m toadflax, yarrow, aster, gromwell, horsetail, ironweed, C sesbania, bulrush, cattail and wintercress.

Similarly, such weeds can be classified as broadleaf C CHX R or grassy weeds. It is economically desirable to control ll l 3 wherein Y is selected from the group consisting of hydrogen, lower alkyl and halogen; R is selected from the group consisting of hydrogen, lower alkyl and lower alkoxy; R is lower alkyl; R, R, R R and R are inde pendently selected from the group consisting of hydrogen and lower alkyl; X is halogen; m is the integer 1; Z and Z are sulfur; and n is an integer from 1 to 2.

2. The compound of claim 1, N-a-chloroacetyl-N- l,3-dithian-2-ylmethyl)-2,6-diethylaniline.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION PATENT NO. t 3,900,497

DA E I August 19 1975 INVEN R( I Sidney B. Richter and John Krenzer It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In Table I, column 12, the rating for the product of Example 18 at l lb/acre on crabgrass should read 4 Signed and Erealed this twenty-first Day Of October 1975 [SEAL] Arrest.-

RUTH C. MASON C. MARSHALL DANN Artesn'ng Officer Commissioner nfPatenIs and Trademarks 

1. A COMPOUND OF THE FORMULA
 2. The compound of claim 1, N- Alpha -chloroacetyl-N-(1,3-dithian-2-ylmethyl)-2,6-diethylaniline. 